Hydrogenation apparatus

ABSTRACT

An apparatus for reacting carbonaceous material such as pulverized coal with heated hydrogen to form hydrocarbon gases and liquids suitable for conversion to fuels wherein the reaction involves injection of pulverized coal entrained in a minimum amount of gas and mixing the entrained coal at ambient temperature with a separate source of heated hydrogen. The heated hydrogen and entrained coal are injected through a rocket engine type injector device. The coal particles are reacted with hydrogen in a reaction chamber downstream of the injector. The products of reaction are rapidly quenched as they exit the reacting chamber and are subsequently collected.

This is a division, of application Ser. No. 871,163, filed Jan. 20,1978, now U.S. Pat. No. 4,243,509 issued Jan. 6, 1981, which is acontinuation of application Ser. No. 689,002, filed May 24, 1976 andsince abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to the field of coal conversion to formhydrocarbon gases and liquid suitable for conversion to fuels.

More particularly, this invention relates to apparatus for reactingcarbonaceous material such as pulverized coal with heated hydrogen toform hydrocarbon liquids suitable for conversion to fuels or for use asa chemical feedstock.

2. Description of the Prior Art

The problem is to react coal directly with hydrogen in such a way as tomaximize the yield of liquid products. A number of researchers haveshown that at the beginning of coal pyrolysis a transient period existsfor a few tenths of a second where the coal is highly reactive towardhydrogen. If excess hydrogen is not available during this period, someof the free-radical pyrolytic fragments will strip molecular hydrogenfrom the aromatic groups while other fragments will polymerize to formunreactive char. The overall effect is a limited yield of liquid andgaseous hydrocarbons, and a large yield of char. If instead, excesshydrogen is present during the critical transient period, many morehydrogenated fragments that are amenable to still further hydrogenationare produced. The overall effect of pyrolysis in hydrogen is a muchlarger yield of liquids and gases, and a lower char yield.

It is generally well known the conversion of coal to liquid or gaseousfuels is achieved by the addition of hydrogen. This may be accomplishedby the direct contact of coal with hydrogen as in the Bureau of MinesHydrane process to produce methane; by a catalyzed liquid-phase reactionwith hydrogen to produce liquid products as in the Synthoil process; orindirectly by reacting coal with steam. Many different processes havebeen proposed and are under development. These schemes vary in themethod of contacting coal and hydrogen or steam, and in the type of coalfeed utilized. A solid such as coal can be contacted with a gas in threebasically different ways. In the first, gas is forced through a fixed orslowly moving bed of solid. Another method of contact is by use of afluidized bed. With sufficiently small solid particles and asufficiently high gas velocity in vertical upward flow the air dynamicdrag forces on the individual particles begin to approach thegravitational forces and the particles themselves begin to move about.The bulk properties of the gas solid mixture then become those of afluid. Because of the improved heat and mass transfer characteristics ina fluidized bed as opposed to a fixed bed, most coal gasificationprocesses now are the fluidized bed variety. Yet another basic categoryof gas solid contacting is entrained flow as in the Bigas process. Inthis regime gas velocities are high enough and particle sizes low enoughthat the solid particles are carried along with the gas stream. Anadvantage of the entrained flow processes is the ability to utilize anygrade or class of coal. Caking coals will agglomerate causing difficultproblems when fed to fluidized or fixed bed systems. Further advantagesof entrained flow with respect to gas production include operation athigh temperatures so that tar production is kept to a minimum,adaptability to slagging conditions and high energy production per unitvolume. The present invention utilizes this type of entrained flow coalconversion process. Heretofore no large scale attempt to use thisapproach for direct hydrogenation of coal has been made.

A patent issued to W. C. Schroeder, U.S. Pat. No. 3,030,297, describes aprocess which comprises heating dry particles of coal entrained in aheated stream of hydrogen at total pressure of about 500-6000 psig froma temperature below about 300° C. to a reaction temperature in the rangeof from about 600° C. to about 1000° C. Two minutes are required to heatthe coal particles to about 600° C. and then two to twenty seconds timeat temperature for hydrogenation. The slow heat-up results from the mainhydrogen stream being utilized to carry the coal into the reactor. Theproducts of reaction are then cooled below reaction temperature toprovide a product comprised of light oil, predominantly aromatic innature, and hydrocarbon gases, primarily methane and ethane, and carbonmonoxide.

This process is disadvantaged in that the coal particles entrained inthe hydrogen are preheated prior to introduction into a heating chamberthus the reaction process is started upstream of the reaction chamberwhich will cause agglomeration and plugging within the conduit carryingthe entrained coal. The present invention overcomes this agglomerationproblem by providing two sources of gas, one source of gas such ashydrogen brings entrained coal into an injector at ambient temperature,and a separate source provides heated hydrogen to an injector whichcontacts the entrained dense phase coal downstream of an injector withina reaction zone thereby starting the hydrogenation process within thereaction chamber and not upstream of the chamber.

Schroeder is further disadvantaged in that he attempts to heat theentrained coal particles through a tube wall. At the mass throughputsspecified in the example, it is doubtful that enough heat could betransferred through the tube wall in a reasonable length to sufficientlyheat the coal and, at the same time, use the tube wall to contain thesystem pressure. This type of reactor does not scale to the necessarylarger diameters for commercial coal conversion reasonably because theheat transfer surface-to-volume ratio decreases rapidly with an increasein size.

Schroeder is still further disadvantaged in that the mixing and theheating takes place in minutes and seconds whereas the present inventionaccomplishes the hydrogenation of the entrained coal in milliseconds andif a uniform flow pattern can be maintained (to avoid back mixing whichwill cause longer residence time and gas production instead of liquids)and if the coal can be dispersed uniformly even on a microscopic scale(to minimize gas diffusion limitations), and if rapid and efficientquenching can be achieved (Schroeder carries the hydrogenated productsthrough a conduit towards a separate quenching chamber whereas thepresent invention quenches the reaction products immediately uponexiting the end of the reaction chamber), then it should be possible tohydrogenate a substantial fraction of the coal to liquid products. Theutilization of rocket engine type injector principles in a coalliquefaction plant as described in the present invention is believed tobe unique and is one of the principal objects of the invention.

Another patent issued to Schroeder et al, U.S. Pat. No. 3,152,063,teaches a process which comprises dispersing pulverized and catalyzedcoal, in the absence of a pasting oil, in hydrogen under a pressure ofabout 500 to 4000 psig, reacting the mixture of coal and hydrogen at atemperature in the range of about 450° to 600° C., for a gas residencetime of less than about 200 seconds, cooling the reaction products andrecovering liquid and gas hydrocarbon products therefrom.

Schroeder teaches passing of catalyzed coal and hydrogen into atwo-stage reactor that consists of a multiplicity of parallel tubesaxially extending within the reactor. The tubes are heated by a sourceof hot gas to start the reaction within the tubes. Vaporized oil and gasproducts are drawn off as well as unused hydrogen to a cooling device.The residual heavier oil and tar products are collected in the bottom ofthe reactor and a source of hydrogen may then be brought in to furtherhydrogenate these heavier products.

This invention is disadvantaged in that the pulverized coal must bepassed through a catalyzing process, sent through a dryer and grinderand finally separated into minute particles by passing the coal througha screening process. The present invention utilizes finely-dividedpulverized coal directly without the foregoing pre-treatment process.

Schroeder's invention is further disadvantaged in that it also utilizesthe carrier hydrogen in the coal passages as the main source ofhydrogen. The heat-up process then takes considerable time as comparedto the present invention in that the carrier gas cannot be pre-heatedprior to entering into a reaction chamber.

Additionally, the invention is disadvantaged in that the coal particlesare heated through a tube or a series of tubes thereby seriouslyaffecting the ability to scale-up the process to commercial productionproportions. A commercial unit would necessarily have to process in theneighborhood of 1000 tons/hour. The Schroeder patents teach a massthroughput of approximately 145 lbs/hr ft.², a very low process rate.For example, in a commercial reactor using the Schroeder process, eachreactor being 15 feet in diameter, 82 reactors would be needed toprocess 1000 tons/hr of coal. In addition, because of the smallsurface-to-volume ratio the reactors would have to be on the order ofone hundred feet long to transfer sufficient heat through the walltransporting the entrained coal particles. One of the most importantadvantages of the high throughput of dense phase coal particles throughthe reactor of the present invention (33,000 lbs/hr ft.²) is that it isscaleable to a commercial size. Two reactors utilizing the principlesset forth in the following specifications, 6-feet in diameter wouldprocess 1000 tons/hr of coal. The heat is supplied directly in thehydrogen so that vessel surface-to-volume ratio is not a limitingfactor.

Although the chemistry of coal pyrolysis and hydrogenation has beenapparent for some time, no well-developed reactor exists whichefficiently utilizes the rapid-reaction regime. Some of the basicreasons for this appear to be a lack of adequate gas/solid injection andmixing technology, difficulty in meeting chemistry and residence timerequirements, and agglomeration and plugging of the reactor.Hydrogenation of raw bituminous coal usually results in agglomeration,so that typical fluidized bed or moving bed reactors cannot be used asheretofore described. In addition, the requirement of short residencetime (less than 1 sec) necessarily restricts the reactor to an entrainedflow type. By maintaining rapid mixing, heat-up, and reaction of thecoal near the point of injection and hot reactor walls, theagglomeration problem can be avoided. The uniform and precise mixing ofextremely large feed streams in time of a few milliseconds is thespecial accomplishment of large rocket engine injectors and one of theprincipal objects of the present invention.

SUMMARY OF THE INVENTION

It is an object of this invention to convert coal particles entrained ina gas in a dense phase to hydrocarbon liquids and gases by hydrogenatingthe coal particles.

More particularly, it is an object of this invention to provide anapparatus which utilizes rocket engine injection and mixing techniquesin an entrained flow reactor to rapidly mix and react a separate streamof heated hydrogen with a dense phase stream of pulverized coal atambient temperature to produce liquid and gaseous hydrocarbons.

It is yet another object of this invention to build and operate ahigh-temperature, coal liquefaction reactor which minimizes secondaryoil and tar decomposition reactions by optimum control of gas-phaseresidence time, and prevents reactor plugging from coal agglomeration byvery rapid dispersion and reaction of the coal while maintaining theinternal reactor wall at high temperature.

A coal liquefaction apparatus is provided which will produce hydrocarbonliquids and gases by hydrogenating pulverized coal with hydrogen byflowing pulverized coal particles entrained in a gas such as hydrogen ina dense phase in a coal flow conduit at ambient temperature toward aninjector adjacent to a reaction chamber and including a heating meansfor heating a separate source of hydrogen. The dense phase pulverizedcoal is injected through the injector into the reaction chamber followedby injecting the heated separate source of hydrogen gas through theinjector into the reaction chamber and means to separate the ambienttemperature dense phase coal particles and the heated hydrogen prior toinjection of the dense phase coal and the heated hydrogen into thereaction chamber to prevent premature hydrogenation of the pulverizedcoal. A quenching means is provided adjacent the reaction chamber torapidly arrest the hydrogenation process at a predetermined time periodwhen the reaction products exit the reaction chamber, and a collectingmeans is provided for collecting the reaction products.

The coal is fed to the reactor at nearly its bulk density so that thequantity of entrained gas is minimized, and the heated hydrogen broughtin separately provides the heat source needed to raise the coal rapidlyto reaction temperatures.

An entrained flow reactor using rocket engine injection and mixingtechniques to react a stream of hot hydrogen with a stream of pulverizedcoal was designed, built, and operated. As an example only, typicalreactor operating conditions were 1000 psig, 1100° F., ≈150 millisecondsresidence time, and 0.36 lb H₂ /lb coal. Approximately 19% of the coalcarbon was converted to a synthetic crude oil having a boiling range of200°-350° C. and a heating value of 15,800 BTU/lb, 9% to gas containingmethane, ethane, and carbon oxides, and 3% to organic compounds in thequench water. The coal throughput rate was approximately 33,000 lbs/hrft² reactor cross section or 11,000 lbs/hr ft³ reactor volume. Theproducts of reaction were rapidly quenched to 220° F. in a distance of 1ft using large flowrates of water through spray nozzles.

Thus, an advantage over the prior art is the use of rocket engineinjection and mixing techniques to rapidly mix and react a stream ofentrained coal with hot hydrogen to produce liquid and gaseoushydrocarbons.

Another advantage of the present invention over the prior art is theminimization of secondary oil and tar decomposition reaction by optimumcontrol of gas-phase residence time by very rapid coal particledispersion and reaction of the coal while maintaining the internalreactor wall at high temperature.

Yet another advantage over the prior art is the prevention of coalagglomeration upstream of the reaction chamber by transporting theentrained dense phase coal in a gas at ambient temperature.

Still another advantage over the prior art is the ability to use acarrier gas other than hydrogen for transporting the coal particles in adense phase to the injector thus minimizing explosion hazards in thecoal feed system due to hydrogen leakage to the atmosphere from movingmechanical parts such as valves, buildup of explosive mixtures ofhydrogen and air in the coal containing vessels, and loss of hydrogenthrough venting when lock hoppers are used.

A still further advantage over the prior art is the immediate quenchingof the hydrogenated coal particles as they exit the end of the reactionchamber thereby maximizing the product yield of liquid and gaseoushydrocarbons.

Another advantage over the prior art is the direct hydrogenation of coalparticles in a reaction chamber as opposed to heating the exterior wallof a tube surrounding the hydrogen and coal particles contained withinthe tube.

The above-noted objects and advantages of the present invention will bemore fully understood upon the study of the following description inconjunction with the detailed drawings.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a flowsheet schematic of the coal liquefaction apparatus;

FIG. 2 is a detailed cross-section of the principal elements of theinvention;

FIG. 3 is an enlarged partially cross-sectioned view of the hot hydrogenand the coal flow coupling upstream of the injector;

FIG. 4 is an enlarged cross-section of the concentric injector;

FIG. 5 is a view of the heater coil element and electrical couplingadjacent the reaction chamber and coal flow tubes;

FIG. 6 is an alternative view of the reaction chamber illustratingdiverging walls from the injector face to the exit plane of the reactortube;

FIG. 7 is an alternative view of an injector illustrating a four-on-oneinjection pattern; and

FIG. 8 is a view taken along lines 8--8 of FIG. 7.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Referring now to FIG. 1, a coal liquefaction unit generally designatedas 10 consists of a nitrogen supply system generally designated as 12that serves as a purge supply source as well as a pressurizing sourcefor a quench water tank system generally designated as 14.

A high pressure coal feeder generally designated as 16 comprises acylindrical vessel 18 suspended from a load cell 20. The coal feeder 16is charged by flowing coal from a low pressure conical tank 22 through atube 24. To charge the high pressure coal feeder 16, the conical tank 22is pressurized to about 55 psig with nitrogen from supply system 12, aball valve 26 at the conical tank bottom is quickly opened wide, and thecoal flows in a dense phase through the tube 24 to the coal feeder 16.The excess nitrogen vents out of the coal feeder through a dust filter28. After the coal feeder 16 is charged, the tube 24 is disconnected andcapped as shown at 27, and the dust filter 28 is disconnected and thepressure relief line 32 connected in its place, as shown in FIG. 1. Ahopper hydrogen feed line 30 from a hydrogen source 48 or inert gas froman inert gas source 50 is opened for subsequent operation. Load cell 20readings before and after charging indicate the quantity of coal in thefeeder. The bottom 19 of the coal feeder 16 is conically shaped with a30° included angle to provide smooth discharging of coal. Coal is fed tothe reactor assembly by opening a ball valve 34 and flowing in a densephase through a feed line 36. The hydrogen or inert gas pressure in thecoal feeder is maintained, for example, about 60 to 70 psi higher thanin the reactor assembly generally designated as 38 so as to provide thedriving force for feeding the coal to the reactor assembly 38. Theweight of hydrogen carried in the coal as a percent of the coal flowrateis about 0.5% when the reaction chamber pressure is 1000 psig. In thecase of inert transport gas, the weight percent transport gas will varyaccording to gas density. The flowrate of coal is about 0.15 pound persecond and the flowrate of hydrogen is about 0.0075 pound per secondwhere hydrogen is used as the carrier gas. Load cell readings areprinted during a test so that the coal feed rate can be continuouslymonitored (not shown). When the feeder ball valve 34 is in a closedposition, nitrogen from nitrogen supply system 12 flowing through a line40 is purged through the feed line 36 to keep it clear and to preventthe coal side of the injector (FIG. 4) from overheating. The portion ofthe coal feed line passing through a top flange 37 and making up part ofan injector assembly 92 (FIG. 3) is typically fabricated from stainlesssteel. Details of the injector assembly 92 are shown in FIGS. 3 and 4.

Pressurized water for a quench system generally designated as 42 issupplied by, for example, a 150 gallon pressurized quench water tanksystem 14. The flow of water can be accurately measured continuouslyduring tests and is varied by changing the pressure on the water tankfrom nitrogen supply system 12. Accurate flow control is possiblebecause the pressure drop across spray nozzles 106 (FIG. 2) is normallyabout 180 psi. In addition, there is about another 130 psi in pressuredrop ahead of the spray nozzles.

It would be obvious to use fluid other than water to quench thehydrogenated products as they exit the reaction chamber such as steam,oil or cold gas (hydrogen).

There are three gas supply systems, one for nitrogen, one for hydrogenand one for an inert gas. The nitrogen supply system 12 supplies thenitrogen bleed to a preheater assembly 39 through a conduit 31 andreactor pressure shells 53, and for purging the coal feed line throughline 40. The flows are controlled by using sonic nozzles (not shown) andvarying the pressure upstream of the nozzles to obtain variousflowrates. The hydrogen source 48 supplies the high pressure coal feeder16 and the preheater assembly 39. The hydrogen flow to the coal feeder16 is on demand and is only measured with an orifice (not shown). Thegas supplied to the coal feeder 16 need not be hydrogen from hydrogensource 48 but may be an inert gas such as nitrogen, carbon dioxide ormixture thereof from inert gas source 50. The hydrogen flow to thepreheater assembly 39 is controlled by a sonic nozzle and upstreampressure regulator (not shown). The hydrogen system may be set up sothat nitrogen can be used in place of hydrogen for purging and leakchecks (not shown).

Product gas from a spherical catch tank 52 flows through a conduit 54 toa liquid separator tank 56 and then through a back pressure regulatorsystem. After the product gas is let down in pressure, the flowrate ismeasured using an orifice and then the gas goes to a burnstack 58through a tube 60. A gas sample bottle system generally designated as 62is connected to the high pressure side through a line 64 of the gassample bottle system 62 and is vented back into the system through aline 66 to burnstack 58. The sample bottle valves 68 are automated toopen in sequence about every 30 to 60 seconds during a test.

The liquid product letdown is controlled by a tank liquid level controlsystem generally designated as 70 that actuates an on-off valve 72. Theflow out of catch tank 52 is regulated by a linear plug valve 74. Thelinear plug valve 74 is basically a variable orifice that is used toprevent the liquid from surging out of catch tank 52 so fast thatpressure control in the reactor assembly 38 is upset. A header of threevalves 76 is used to select which of drums 78 is to receive the liquidproduct.

A more detailed drawing of the hydrogen preheater assembly generallydesignated as 39 is presented in FIGS. 2 and 5 and of the reactorassembly generally designated as 38 is presented in FIG. 2. The hydrogenpreheater assembly is contained within a pressure shell 41 and thepreheater coil 43 is a stainless steel tube through which an electriccurrent is passed as hydrogen passes through it. The preheater coil 43is thin walled and small in diameter at end 45 and heavy walled andlarger in diameter at end 47. As the hydrogen enters end 45 it isrelatively cool and as it progresses down through helical-shapedpreheater coil 43 it heats up and expands. The variable I.D. and wallthickness of the coil compensates for this expansion of hydrogen. Sevenmotor-generator sets (not shown) supply about 600-800 amps to copperstud conductors 77 and 79 connected to plate 80 through the wall 49 witha power input up to 150 Kw. The heat transfer from theresistively-heated wall 49 to the pressurized hydrogen entering end 45of preheater coil 43 through hydrogen feed line 30 is excellent and hasdemonstrated efficiencies of about 99%. Since the tube wall strength isvery low at the heater operating temperatures (the wall is about 200° F.hotter than the hydrogen at the exit 47 of the tube 43), the preheatercoil 43 is contained in a pressure shell 41 made from, for example,carbon-steel pipe and 600 lb flanges 82 and 84. The void space 86 in thepressure shell 41 is stuffed with, for example, a very low thermalconductivity insulation 87 such as Fibrefrax, a product of CarborundumCorporation, Refractories and Insulation Division, Fibrefrax Branch,Niagra Falls, New York, and is purged continuously with about 5 SCFM ofnitrogen at about 1000 psig. The copper stud conductors 77 and 79, plate80, and inlet end 45 of the preheater coil 43 are electrically isolatedfrom the pressure shell 41 and serve as the positive connection to themotor generator sets. The ground connection is made to another end 51 ofthe pressure shell 41 through the blind stainless steel flange 88 thatis sandwiched between the two carbon steel, weld-neck flanges 84 and 85.A thermocouple 90 is immersed in the gas exiting the preheater assembly39, and a pressure transducer (not shown) is connected to a similar portin the flange.

In a similar fashion, referring to FIG. 2, the reactor tube 98 andinjector assembly generally designated as 92 are enclosed in a pressureshell 53 so that the hot reactor tube walls 94 experience very littlestress while at high temperature. The reactor 98 is supported by theinsulation 87 and slip fits through a hole in the insulation supportplate 96 so that thermal elongation of the reactor tube 98 is allowed.The preheater assembly 39 is connected to the injector assembly 92 via astainless steel coiled tube 100. This tube is coiled so that it canthermally elongate without applying a force against the injectorassembly 92, possibly bowing the reactor tube 98. The reactor tube 98and injector assembly 92 can easily be removed from the pressure shell53 by removing the top flange 37 and a small amount of insulation 87.Several bosses 102 along the side of the pressure shell 53 permitthermocouple measurements along the reactor outside wall, and onedirectly inside the bottom of the reactor tube 98 near exit plane 99.

The quench zone 104 consists, for example, of 3 rows of 4 full-conespray nozzles 106 that screw into the quench zone pipe wall 108 from theoutside. As the reaction products exit the reactor tube 98, they arequenched immediately with water sprays supplying water at about 3 to 6gpm. Enough spray water is used to reduce the product temperature toabout 200° F. The liquid, gas, and solids are forced down into sphericalcatch tank 52 (FIG. 1) where the gas separates and exits. The liquidlevel control system 70 (FIG. 1) is used to maintain a liquid level inthe spherical catch tank 52 and to let down the slurry product intodrums 78 (FIG. 1). Vent line 71 connects to the liquid level controlsystem 70.

FIGS. 3 and 4 illustrate in more detail the injector assembly 92 andreactor tube 98 combination wherein a stream of hot (1500°-2000° F.)hydrogen is reacted with a stream of pulverized coal. The injectorassembly generally designated as 92, for example, consists of a housingbody 110 that is separable from a coal feed line assembly 112 and thereactor tube 98 by a pair of, for example, AN type nuts 114 and 116. Thecoal feed line assembly 112 consists of 3 tubes, an outer shell tube130, an insulation tube 118, and a post tube 120. The post tube 120 is3/8 inch O.D. (Dimension "D" FIG. 4)×0.083 inch wall 321, stainlesssteel. A 0.55 inch length of end 121 of the post tube 120 is machined toform end 121 to 0.254 inch O.D. (Dimension "I" FIG. 4)×0.020 inch wall.The entire injector assembly 92 is contained within the pressure shell53 (FIG. 2). The post tube 120 extends through top flange 37 via apacking gland fitting such as a 3/8 inch Conax fitting 105 made by ConaxCorporation of Buffalo, New York, and is coupled with coal feed line 36outside of the pressure shell 53. End 121 of the post tube 120 extendsconcentrically within a separate cone 122 that is connected to housingbody 110 by AN nut 116. An annulus 124 (FIG. 4) is defined between innerwall 123 of cone 122 and outer surface 125 of end 121 of post tube 120.Annulus 124 is 0.350 inch O.D. with a gap of 0.048 inches (Dimension "G"FIG. 4) to the outer surface 125 of end 121 of the post tube 120. End121 is recessed 0.212 inch (Dimension "F"). Three wire spacers 117 arebrazed to end 121 to center the post tube 120 and end 121 in the annulus124. The post tube 120 is supported as it passes through a plate 115 bya 3/8 inch Conax fitting 135 that is screwed into plate 115. Theinsulation tube 118 is 1 inch O.D.×0.049 inch wall, 321 stainless steeland terminates at end 119 in a cone that diverges toward but is notaffixed to the outer wall of the post tube 120 near end 121. End 113 oftube 118 is affixed to plate 115. An annulus 126 is defined by an outersurface 127 of tube 120 and an inner surface 128 of tube 118. Theannulus 126 is filled with insulation material 87. The outer shell tube130 is a structural member that houses concentric tubes 118 and 120 andconnects at a first end 132 to plate 115 and at the other end 134 tohousing body 110 by nut 114. Tube 130 is 1.5 inch O.D.×0.049 inch wall,321 stainless steel. An annulus 136 is defined by an outer surface 138of tube 118 and an inner surface 140 of housing body 110. The annulus136 serves to direct a hot hydrogen exterior port 111 toward annulus 124and out injector assembly 92 (FIG. 4). An annulus 131 is defined byouter surface 138 of tube 118 and inner surface 129 of tube 130 and isfilled with insulation 87 that is kept from falling in annulus 136 by asleeve 133. The reactor tube 98 (FIG. 3) is 1.5 inch O.D.×0.049 inchwall (Dimension "B", 321 stainless steel tube, is 3 feet long (Dimension"A"), and is connected to the housing body 110 by nut 116. The overallinjector assembly 92 is about 1 ft long (Dimension "C").

In operation, the coal liquefaction plant functions in the followingmanner: A pulverized bituminous coal such as Kentucky hvAb may beutilized. Other types of pulverized coal such as lignite andsub-bituminous may also be used. The coal is typically 70% less than 74microns in size (200 mesh coal) and is fed into high pressure coalfeeder 16. The average coal particle size is 40 to 50 microns. A quarterinch line approximately 20 feet long directs dense phase coal from valve34 into post tube 120 outside of top flange 37 towards the injectorassembly 92. The pressure shells 41 and 53 are pressurized with nitrogento approximately 1000 psig from nitrogen supply system 12. Typically, a70 psi differential between coal feeder 16 and the pressure shells 41and 53 is maintained to encourage coal flow in a dense phase throughfeed line 36 into the injector assembly 92. In other words, the pressurewithin the coal feeder is approximately 1070 psig during operation. Inthis specific example hydrogen from hydrogen source 48 is directedtowards the coal feeder 16 through hydrogen feed line 30 and the ratioof hydrogen to coal is about 0.005 lbs of hydrogen per pound of coal.Obviously, an inert gas may be utilized in place of the hydrogen withthe pulverized coal from inert gas source 50 to the coal feeder 16.Hydrogen is additionally fed from hydrogen source 48 through a conduit29 into the hydrogen preheater assembly 39. The hydrogen is directedinto a 321 stainless steel preheater coil 43 at end 45. The coil 43 atend 45 is 1/4 inch O.D.×0.035 inch wall and as the helix progresses downthe coil 43 it transitions into a 5/16 inch O.D.×0.049 inch wall coiland from there into a 3/8 inch O.D.×0.083 inch wall coil. The hydrogenexits coil 43 at end 47 towards coiled tube 100 which directs hothydrogen into the injector assembly 92. The hydrogen flowrate is 10 to50 percent of the flowrate of dense phase coal. The coil is about 260inches long in this example. The hydrogen is typically fed into coil 43at the rate of 0.025 lbs per second. At startup the dense phase coal isflowed through feed line 36 into the post tube 120 outside top flange 37and into the injector assembly 92 followed by introduction of hothydrogen through the preheater coil 43. The hydrogen exits the heatedcoil in a temperature range between 1500° and 2000° F. (a typicaltemperature is 1650° F.) adjacent the injector assembly 92. Typically,in the foregoing example the reaction temperature within the chamber byreactor tube 98 is found to be about 1100° F. with a residence time ofthe pulverized coal within the reactor tube 98 of about 150 millisecondswhen the hot hydrogen flowrate is 0.36 lbs of hydrogen per pound ofcoal. The reaction time in reactor tube 98 may be between 10 and 500milliseconds for the hydrogenation process. As can be seen from theabove, with a typical reaction temperature of about 1100° F. and ahydrogen temperature range of 1500°-2000° F., the hydrogen temperatureis from 400° to 900° F. in excess of the typical reaction temperature.

It is desirable to promote better mixing to assure that hot hydrogenmoves past the coal particles within the reactor tube 98. For example,the hot hydrogen velocity exiting the injector assembly 92 isapproximately 1000 ft/second while the velocity of the dense phaseentrained coal exiting the injector is about 7 ft/second. Within theseparameters approximately 19 to 20% of the coal carbon is converted intoa synthetic crude oil having a boiling range of about 200°-350° C. and aheating value of 15,800 BTU per lb, 9% to gas containing methane,ethane, and carbon oxides, and about 3% to organic compounds in thequench water. The coal throughput rate is approximately 33,000 lbs perhour ft² reactor cross-section or 11,000 lbs per hour ft³ reactorvolume. The products of reaction are rapidly quenched to about 225° F.downstream of exit plane 99 of reaction tube 98 in a distance of about 1ft, the reaction products passing by water spray nozzles 106 in thequench zone below the reaction chamber defined by reactor tube 98. Thewater flowrate through the multiplicity of water spray nozzles is from 2to 6 gallons per minute. The products are then moved into the catch tank52 and from there to the various drums 78 where the solids arecollected, the gas and by-products being directed into separator tank 56and the by-products being directed through burnstack 58.

It would be obvious to use other means to heat the hydrogen beingseparately directed to the injector assembly 92 other than use of highelectrical current to heat up a coil which is transporting the hydrogen.For example, a conventional fuel fired furance or heater could beutilized to heat up a coil tube containing hot hydrogen. Many othermethods to heat hot hydrogen are within the state of the art.

Turning now to FIG. 6 an alternative reactor tube 141 is illustratedwherein one end of the reaction chamber connected to the injectorassembly 92 at end 142 begins a diverging wall section which divergestowards end 144 adjacent plate 146. The diverging walls defining areaction chamber 150 tend to discourage sticking of the partiallyhydrogenated products passing through the reactor tube 141, thusminimizing any tendency to plug.

FIGS. 7 and 8 disclose a different type of injector commonly known inthe rocket engine field as a four-on-one injector. The injector consistsof a center post 154 which transports dense phase coal particles andwhich is supported within an upper plate 156 and a bottom injector plate160. The inner face 157 of plate 156 and the inner face 158 of injectorplate 160 define an annular chamber 162 which directs hot hydrogenentering a conduit 164 from the preheater assembly into the chamber. Athermal insulator 159 is provided around the center post 154 so thatcoal particles transported within center post 154 are not prematurelyheated. The injector plate 160 has drilled therein a series of fourorifices 166 equidistantly spaced around the injector (FIG. 8) each ofthe orifices having an impingement angle with respect to the center lineof the center post 154 of approximately 30° which facilitates greatermixing of the minute coal particles exiting center post 154 with theimpingeing hot hydrogen downstream of the injector face. FIG. 8 betterdepicts the relationship of the orifices with respect to the center post154.

It would be obvious to configure any number of gas streams on thecentral coal stream with different impingement angles, all of which arewell within the state-of-the-art particularly in the rocket enginefield.

It will, of course, be realized that various modifications can be madein the design and operation of the present invention without departingfrom the spirit thereof. Thus, while the principle, preferredconstruction and mode of operation of the invention have been explainedand what is now considered to represent its best embodiment has beenillustrated and described, it should be understood that within the scopeof the appended claims, the invention may be practiced otherwise than asspecifically illustrated and described.

We claim:
 1. A hydrogenation apparatus having a single reaction chamberfor reacting hydrogen and a pulverized carbonaceous material at adesired hydrogenation reaction temperature to form desired gaseous andliquid hydrocarbon reaction products, said apparatus comprising:a sourceof hydrogen; heating means for heating said hydrogen to a temperatureseveral hundred degrees Fahrenheit above that of the carbonaceousmaterial and that of the desired hydrogenation reaction temperature; anunimpeded flow-through single reaction chamber defining a singlereaction zone, said reaction zone providing for the unimpededhigh-velocity entrained flow therethrough of said hot hydrogen andcarbonaceous material and reaction products formed therefrom, saidchamber having opposite ends and having a length sufficient to providefor a residence time of said hot hydrogen and pulverized carbonaceousmaterial in said reaction zone substantially equal to a reaction time ofup to about 500 milliseconds and having a cross-sectional areasufficient to provide a high entrained flow cross-sectional throughputthrough said reaction zone of pulverized carbonaceous material in saidhot hydrogen; injector means adjacent one end of said reaction chamber,said injector means including (a) means for introducing said pulverizedcarbonaceous material into said reaction zone, (b) means for introducingsaid heated hydrogen into said reaction zone in an amount sufficient torapidly heat said carbonaceous material to the desired hydrogenationreaction temperature in said reaction zone and at a high velocity of atleast several hundred feet per second in excess of that of saidcarbonaceous material and to ensure rapid and uniform mixing with saidcarbonaceous material and to provide said high entrained flowcross-sectional throughput through said reaction zone, and (c)insulating means for maintaining said heated hydrogen thermallyseparated from said carbonaceous material prior to said mixing toprevent agglomeration of said carbonaceous material; and quenching meanslocated adjacent the other end of said reaction chamber for rapidlyquenching the reaction products exiting said reaction chamber to arrestsaid hydrogenation reaction.
 2. The apparatus of claim 1 wherein saidcross-sectional area is sufficient to provide a high entrained flowcross-sectional throughput through said reaction zone of not less thanabout 33,000 lbs./hr. ft.² of pulverized carbonaceous material in saidhot hydrogen.
 3. The apparatus of claim 1 wherein said means (a) and (b)of said injector means consist of a concentric tube injector wherein theinner tube thereof is the coal flow injecting tube and the outer tubethereof is the heated high velocity hydrogen injecting tube.
 4. Theapparatus of claim 1 wherein said means (a) and (b) of said injectormeans consist of a four-on-one-injector, said injector having a centerorifice therein to flow said coal therethrough, said injector furtherhaving four orifices therein equidistantly spaced around said centerorifice at an angle with respect to said center orifice to flow hothydrogen therethrough and impinge said hot hydrogen at a high velocityon said coal downstream of said injector in said reaction chamber. 5.The apparatus of claim 1 wherein said heating means for heating hydrogenis capable of heating said hydrogen to a temperature of 400° to 900° F.above the desired hydrogenation reaction temperature and said quenchingmeans has associated therewith expansion means for expanding the flowcross-section of reaction products exiting said reaction chamber tosubstantially reduce the flow velocity of said reaction products.